JPH033690B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photocurable composition. [Prior Art] Currently, photocurable compositions containing urethane poly(meth)acrylate are being intensively researched and commercialized in various markets. [Problems to be Solved by the Invention] However, the photocurable compositions containing various urethane poly(meth)acrylates currently available on the market are not sufficiently applicable to various uses. So, a new urethane poly(meta)
There is a strong need to provide photocurable compositions containing acrylates. Therefore, providing photocurable compositions containing novel urethane poly(meth)acrylates to these markets is extremely useful for the advancement of various applications. [Means for Solving the Problem] The present invention provides: (A) a urethane poly(meth)acrylate consisting of a reaction product of the following components (a), (b) and (c); (a) the following [ ] compound (R ₁ in formula [] represents CH ₃ , C ₂ H ₅ or C ₃ H _7. ) (b) Organic polyisocyanate ... [] (c) The following [], [] or/and [] Compound (R ₂ and R ₃ in formula [] represent H or CH _3. ) (R ₂ and R ₃ in the formula [] represent H or CH ₃
(n is 1 to 20) A compound that is an esterified product of polyol and (meth)acrylic acid and has at least one OH group... [] and (B) A photopolymerization initiator. The present invention relates to a photocurable composition. Urethane poly(meth)acrylate (A) is produced by converting components (a) and (b) into urethane, and then converting them into poly(meth)acrylate with component (c). The compound [ ] is obtained by condensation of 2,2-dimethyl-3-oxypropanal and trimethylolalkane. A particularly preferred trimethylolalkane is trimethylolpropane. Examples of organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. , dimer acid diisocyanate, etc. Particularly preferred organic polyisocyanates are hexamethylene diisocyanate and isophorone diisocyanate. Examples of the compound [ ] include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of compounds in [] include monohydroxypolycaprolactone with acrylate or methacrylate end groups (Plaxel FA-1, FA-2, FM-1, FM-2, etc. manufactured by Daicel Chemical Industries, Ltd.);
There is. Examples of compounds in [] include glycerin, trimethylolpropane, 1,2,4-
A poly( Meta) acrylate. In addition, at least one polycaprolactone polyol obtained by adding epsilon caprolactone to the above polyol is used.
Examples include poly(meth)acrylate having OH groups. A particularly preferred compound [ ] is pentaerythritol triacrylate. The above-mentioned urethanization reaction can be carried out in the presence of a known catalyst that promotes urethane formation, such as a tertiary amine, dibutyltin dilaurate, dioctyltin dilaurate, etc., in order to promote the reaction between isocyanate groups and hydroxyl groups. Also,
In this urethanization reaction, a slight excess of either reactant can be used, if desired, in procedures known to those skilled in the art, which are inert under the reaction conditions and which also act as viscosity reducing agents. It can be carried out in an organic solvent. These organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and ethers such as isopropyl ether and ethyl ether. There are suitable solvents. Often the reaction is carried out in a reactive diluent that can be carried in the formulation, used as a formulation of the photocurable composition, and incorporated into the composition to be cured. It can be carried out. Examples of such reactive diluents include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ) acrylate, neopentyl glycol di(meth)
Examples include acrylate, tetrahydrofurfuryl acrylate, and styrene. In addition, the reaction temperature of this urethanization reaction is room temperature to
The temperature is 100°C, preferably 50-80°C. Then, in the next poly(meth)acrylation reaction, a slight excess of component (c) can be used with respect to the compound having terminal isocyanate groups obtained in the urethanization reaction. In this reaction, in order to prevent gelation due to radical polymerization during the reaction, 50 to 2000 PPm (based on the compound having a terminal isocyanate group) of phenothiazine, hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol, P-
It is preferable to add a polymerization inhibitor such as benzoquinone. In addition, the reaction temperature of this poly(meth)acrylate reaction is room temperature to 100°C, preferably 50 to 80°C.
It is. Urethane poly(meth) synthesized in this way
Acrylate (A) can be used as a base resin in coating and ink compositions or as a base resin for other monomers (1,
6-hexanediol diacrylate, N-vinyl-2-pyrrolidone, styrene, etc.) or polymers (epoxy acrylate, polyester acrylate, etc.), fillers and other additives. Photoinitiators (B) are generally known to those skilled in the art and include, for example, benzophenone, acetophenone, 2-chlorothioxanthone, benzoin,
Benzyl, 2-ethylanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1
- Many types can be mentioned, such as on. The photoinitiator (B) is incorporated into the photocurable composition at a concentration of 0.1 to 10% by weight. Photocurable compositions can be applied by conventional means and photocured by actinic radiation, such as ultraviolet light. [Example] Hereinafter, the present invention will be explained in detail with reference to Synthesis Examples and Examples. In addition, the measurement method in the examples was performed as follows. (1) Pencil hardness...Pencil hardness according to JIS K 5651-1966 (2) Scratch test...Scratch test with #000 steel wool ○...Even when lightly rubbed, the surface hardly gets scratched. △…If you rub it lightly, the surface will be slightly scratched. ×... Even if you rub it lightly, the surface will be seriously scratched. Synthesis Example 1 In one reactor equipped with a stirrer, a temperature controller, a thermometer, and a condenser, a compound of [ ] having the following structure, which is a condensate of 2,2-dimethyl-3-oxypropanal and trimethylolpropane, is prepared. 119.7 parts and 222.3 parts of isophorone diisocyanate was charged.
The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 12.2% free acid isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 8 hours. Next, while stirring, 127.7 parts of hydroxyethyl acrylate, 58.8 parts of 1,6-hexanediol diacrylate (HDDA manufactured by Nippon Kayaku), and a monoacrylate prepared by adding 1 mole of epsilon caprolactone to tetrahydrofurfuryl alcohol (TC-110S manufactured by Nippon Kayaku) were added. ), 0.23 part of hydroquinone monomethyl ether, and 0.09 part of di-n-butyltin dilaurate. This reaction temperature is also 70 to 75
This was done while maintaining the temperature at ℃. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As reaction products, 587 parts of a monoacrylate diluted product of 1,6-hexanediol diacrylate, which is a hydroxyethyl acrylate adduct obtained by adding isophorone diisocyanate to the compound [], and 1 mole of epsilon caprolactone added to tetrahydrofurfuryl alcohol were obtained. This product has the following properties. Hue (APHA) 80 Specific gravity (25℃) 1.088 Viscosity (25℃) 546CPS Synthesis example 2 2,2-dimethyl-
119.7 parts of the compound [] having the following structure, which is a condensate of 3-oxypropanal and trimethylolpropane; 222.3 parts of isophorone diisocyanate was charged.
The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 12.2% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 8 hours. Next, while stirring, 143 parts of hydroxypropyl acrylate, 161.8 parts of diacrylate obtained by adding 4 moles of ethylene oxide to bisphenol A (R-551, manufactured by Nippon Kayaku), and N-vinyl-2-pyrrolidone (NV2-P, manufactured by GAF) were added. 161.8 parts of hydroquinone monomethyl ether, 0.24 parts of di-n-butyltin dilaurate were charged. This reaction temperature also
This was carried out while maintaining the temperature at 70 to 75°C. The reaction products were continued until the reaction was completed, as indicated by about 0.3% or less of free isocyanate groups. Diacrylate and N-vinyl-2-
808 parts of pyrrolidone dilution were obtained. This product has the following properties. Hue (Gardner) 4 Specific gravity (25℃) 1.107 Viscosity (25℃) 15340CPS Synthesis example 3 In the same reactor as synthesis example 1, a condensate of 2,2-dimethyl-3-oxypropanal and trimethylolpropane was added. 47.9 parts of the compound [] having the following structure and 88.9 parts of isophorone diisocyanate was charged.
The reaction temperature of this blend was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 12.2% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 8 hours. Next, with stirring, diacrylate (Nippon Kayaku HX-
220) 281.8 parts of monoacrylate with 1 mole of ethylene oxide added to phenol (Nippon Kayaku R-
561), 0.19 parts of hydroquinone monomethyl ether, and 0.08 parts of di-n-butyltin dilaurate were charged. This reaction temperature was also maintained at 70 to 75°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As reaction products, the compound [] is added with isophorone diisocyanate, pentaerythritol triacrylate adduct, neobentyl glycol hydroxypivalate, diacrylate with 2 moles of epsilon caprolactone added, and monoacrylate diluted with 1 mole of ethylene oxide added to phenol. Obtained 939 copies. This product has the following properties. Hue (APHA) 70 Specific gravity (25℃) 1.120 Viscosity (25℃) 502CPS Synthesis example 4 In the same reactor as synthesis example 1, a condensate of 2,2-dimethyl-3-oxypropanal and trimethylolpropane was added. 119.7 parts of the compound [] having the following structure and 168 parts of hexamethylene diisocyanate was charged. The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 14.6% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 7 hours. Then, with stirring, 127.7 parts of hydroxyethyl acrylate, 52 parts of 1,6-hexanediol diacrylate (HDDA, manufactured by Nippon Kayaku), and a monoacrylate obtained by adding 1 mole of epsilon caprolactone to tetrahydrofurfuryl alcohol (TC-110S, manufactured by Nippon Kayaku). 52 parts and 0.21 parts of hydroquinone monomethyl ether and di-n-butyltin dilaurate
I prepared 0.08 parts. This reaction temperature was also maintained at 70 to 75°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As a reaction product, 519 parts of a diluted monoacrylate of 1,6-hexanediol diacrylate, which is the hydroxyethyl acrylate adduct of the compound [] added with hexamethylene diisocyanate, and 1 mole of epsilon caprolactone added to tetrahydrofurfuryl alcohol, was obtained. . This material has the following properties. Hue (APHA) 70 Specific gravity (25℃) 1.131 Viscosity (25℃) 18800CPS Synthesis example 5 2,2-dimethyl-
Compound 119.79 with the following structure, which is a condensate of 3-oxypropanal and trimethylolpropane, and 168 parts of hexamethylene isocyanate was charged. The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 14.6% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 7 hours. Then, with stirring, 1 mol of epsilon caprolactone adduct of hydroxyethyl acrylate (Plaxel FA-1 manufactured by Daicel Chemical Industries, Ltd.) 253.1
diacrylate with 4 moles of ethylene oxide added to bisphenol A (Nippon Kayaku R-551)
180.4 parts of N-vinyl-2-pyrrolidone (NV2-P manufactured by GAF), 0.27 parts of hydroquinone monomethyl ether, and di-n-butyltin dilaurate.
I prepared 0.11 parts. This temperature was also maintained at the above reaction temperature of 70 to 75°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As a reaction product, the compound [] is added with hexamethylene diisocyanate, hydroxyethyl acrylate is added with 1 mole of epsilon caprolactone, diacrylate of bisphenol A is added with 4 moles of ethylene oxide, and N-vinyl-2-pyrrolidone diluted. Got 900 copies. This material has the following properties. Hue (Gardner) 4 Specific gravity (25℃) 1.120 Viscosity (25℃) 3096CPS Synthesis example 6 2,2-dimethyl-
47.9 parts of the compound [] having the following structure, which is a condensate of 3-oxypropanal and trimethylolpropane; 67.2 parts of hexamethylene diisocyanate was charged. The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 14.6% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 7 hours. Then, with stirring, diacrylate (Nippon Kayaku HX
-220) 265.5 parts of monoacrylate with 1 mole of ethylene oxide added to phenol (Nippon Kayaku R
-561), 0.18 part of hydroquinone monomethyl ether, and 0.07 part of di-n-butyltin dilaurate were charged. This reaction temperature was also maintained at 70 to 75°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As reaction products, the compound [] is added with hexamethylene diisocyanate, pentaerythritol triacrylate adduct, neopentyl glycol hydroxypivalate, diacrylate with 2 moles of ibusilone caprolactone added, and monoacrylate diluted with 1 mole of ethylene oxide added to phenol. Obtained 884 copies. This material has the following properties. Hue (APHA) 60 Specific gravity (25℃) 1.121 Viscosity (25℃) 410CPS Synthesis example 7 2,2-dimethyl-
47.9 parts of the compound [] having the following structure, which is a condensate of 3-oxypropanal and trimethylolpropane; 63.2 parts of xylylene diisocyanate was charged. The reaction temperature of this mixture was maintained at 70 to 75°C. The reaction was continued until completion as indicated by 15.1% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 7 hours. Then, with stirring, 2 moles of epsilon caprolactone adduct of hydroxyethyl acrylate (Plaxel FA-2 manufactured by Daicel Chemical Industries) 151.3
diacrylate with 4 moles of ethylene oxide added to bisphenol A (Nippon Kayaku R-551)
87.5 parts of N-vinyl-2-pyrrolidone (NV2P manufactured by GAF), 0.13 parts of hydroquinone monomethyl ether, and di-n-butyltin dilaurate.
I prepared 0.05 parts. This reaction temperature was also maintained at the above reaction temperature of 70 to 75°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As a reaction product, an adduct of the compound [] with xylylene diisocyanate, an adduct of 2 moles of epsilon caprolactone with hydroxyethyl acrylate, a diacrylate of bisphenol A with 4 moles of ethylene oxide, and N-vinyl-2
- 437 parts of pyrrolidone dilution were obtained. This material has the following properties. Hue (Gardner) 4 Specific gravity (25°C) 1.137 Viscosity (25°C) 3032CPS Table 1 shows the property values of the reaction products obtained in Synthesis Examples 1 to 7 above.

[Table] Example 1 A photocurable composition was prepared by adding 5 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Geigy) to 100 parts of the compound obtained in Synthesis Example 1. This composition was applied onto a steel plate panel, and irradiated with light using a 2KW high-pressure mercury lamp at a distance of 8 cm in height and at a line speed of 18 m/min. The composition reached a tack-free state after being irradiated twice at the above rate. The pencil hardness of this cured film was 2H, and the steel wool abrasion test was X. Example 2 A photocurable composition was prepared by adding 5 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure 1173, manufactured by Merck & Co.) to 100 parts of the compound obtained in Synthesis Example 2. This composition was applied onto a steel plate panel, and irradiated with light using a 2KW high-pressure mercury lamp at a distance of 8 cm in height and at a line speed of 18 m/min. The composition reached a tack-free state after one irradiation at the above rate. The pencil hardness of this cured film was 4H, and the steel wool abrasion test was X. Example 3 To 100 parts of the compound obtained in Synthesis Example 3, 5 parts of phenylglyoxylic acid ester (Vaicure-55, manufactured by Stouffer Japan) was added to prepare a photocurable composition. This composition was applied onto a steel plate panel, and irradiated with light using a 2KW high-pressure mercury lamp at a distance of 8 cm in height and at a line speed of 18 m/min. The composition reached a tack-free state after four irradiations at the above rate. The pencil hardness of this cured film was 4H, and the steel wool abrasion test was X. Example 4 1-Hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy) was added to 100 parts of the compound obtained in Synthesis Example 4.
A photocurable composition was prepared by adding 5 parts of Irgacure 184). This composition was applied onto a steel plate panel, and irradiated with light using a 2KW high-pressure mercury lamp at a distance of 8 cm in height and at a line speed of 18 m/min. The composition reached a tack-free state after three irradiations at the above rate. The pencil hardness of this cured film was 3H, and the steel wool abrasion test was X. Example 5 A photocurable composition was prepared by adding 5 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure 1173, manufactured by Merck & Co.) to 100 parts of the compound obtained in Synthesis Example 5. This composition was applied onto a steel plate panel, and irradiated with light using a 2KW high-pressure mercury lamp at a distance of 8 cm in height and at a line speed of 18 m/min. The composition reached a tack-free state after one irradiation at the above rate. The pencil hardness of this cured film was 6H, and the steel wool abrasion test was ○. Example 6 To 100 parts of the compound obtained in Synthesis Example 6, 5 parts of phenylglyoxylic acid ester (Viquiure-55, manufactured by Stouffer) was added to prepare a photocurable composition. This composition was applied on a steel plate panel and 2KW
Using a high-pressure mercury lamp, a distance of 18 m at a height of 8 cm /
The light was irradiated at a line speed of minutes. The composition reached a tack-free state after being irradiated five times at the above rate. The pencil hardness of this cured film was 5H, and the steel wool abrasion test was △. Example 7 To 100 parts of the compound obtained in Synthesis Example 7, 5 parts of phenylglyoxylic acid ester (Viquiure-55, manufactured by Stouffer) was added to prepare a photocurable composition.
This composition was applied onto a steel plate panel and irradiated with light using a 2 KW high pressure mercury lamp at a line speed of 18 m/min at a distance of 8 cm. The composition reached a tack-free state after being irradiated six times at the above rate. The pencil hardness of this cured film was 3H, and the steel wool abrasion test was x. Table 2 shows the evaluation results obtained in Examples 1 to 7 above.

〔Effect of the invention〕

The photocurable composition of the present invention has excellent hardness and can be used in inks or coating compositions.

Claims (1)

[Scope of Claims] 1 (A) Urethane poly(meth)acrylate consisting of a reaction product of the following components (a), (b) and (c): (a) The following compound [] (R ₁ in formula [] represents CH ₃ , C ₂ H ₅ or C ₃ H _7. ) (b) Organic polyisocyanate ... [] (c) The following [], [] or/and [] Compound (R ₂ and R ₃ in formula [] represent H or CH _3. ) (R ₂ and R ₃ in the formula [] represent H or CH ₃
(n is 1 to 20) A compound that is an esterified product of polyol and (meth)acrylic acid and has at least one OH group... [] and (B) A photopolymerization initiator. A photocurable composition.